This invention relates to the use of quasi-crystalline alloys for the absorption of infra-red radiation as well as devices for the absorption of infra-red radiation comprising an element made of a quasi-crystalline alloy.
Various types of devices are known that absorb infra-red radiation. In particular, devices are known that carry out the photo-thermal conversion of the infra-red radiation, in which the absorbed light energy is converted into heat. These are notably solar radiation collectors which include a layer of a paint that absorbs the infra-red radiation, deposited on a substrate. Among these devices, one may mention, in particular, collectors with a heat exchange medium or the Trombe wall. In these devices, the heat is taken from the absorbent medium through the substrate, assumed to be a good thermal conductor, by a heat exchange fluid, from which the collected energy is extracted. In general, said paints are made up of organic materials containing absorbent pigments or metal powders which are very finely divided and bonded by an organic additive. Metals can only be used in a very finely divided state, or possibly in the form of a massive element having a very high surface roughness since they are strongly reflecting in the massive state and smooth. However such materials show a poor resistance to external attack and are damaged by mechanical scratching, wear or corrosion. Because of this, they must be protected against attack, for example by glass screens, which increases the price and decreases the durability of them. Furthermore, the interface formed between the absorbing paint and its substrate plays a decisive role in the flow of heat transmitted to the heat exchange fluid and in the life span of the device. Devices are also known in which the infra-red radiation is converted into electrical signals. Among these devices, one may mention bolometers, in which the infra-red radiation causes a variation in the resistance of metallic or semi-conductor elements. The material used for the absorption of the infra-red radiation must have a high electrical resistivity, a high temperature coefficient and a low thermal conductance.
One can also mention, thermal probes (thermocouples) in which the e.m.f. of a pair of conductors of a different kind is measured.
For all these types of infra-red radiation sensors used as detectors, it is necessary to have a low dark current, which means that they are often placed inside a cooled enclosure intended to reduce thermal excitation in the materials and to reduce the flow of ambient radiation.
Furthermore, quasi-crystalline alloys are known, which are alloys made up of one or more quasi-crystalline phases. By quasi-crystalline phase, one understands a quasi-crystalline phase in the strict sense or a phase that approximates to one. A quasi-crystalline phase in the strict sense is a phase that has a symmetry of rotation normally incompatible with the symmetry of translation, that is to say a rotation axis symmetry of order 5, 8, 10 or 12, these symmetries being revealed by the diffraction of the radiation. By way of example, one can mention the icosahedric phase of point group m3 5 and the decagonal phase of a point group 10/mmm. An approximating phase or an approximating compound is a true crystal to the extent that its crystallographic structure remains compatible with the symmetry of translation, but which has, in the electron diffraction image, diffraction diagrams the symmetry of which is close to rotation axes 5, 8, 10 or 12. By way of example, one can mention the orthorhombic phase O1, characteristic of an alloy having the atomic composition Al65Cu20Fe10Cr5, the lattice parameters of which are: a0(1)=2.366, b0(1)=1.267, c0(1)=3.252 in nanometers. This orthorhombic phase O1 is said to be approximate to the decagonal phase. Furthermore, it is so close that it is not possible to distinguish its X-ray diffraction diagram from that of the decagonal phase. One can also mention the rhombohedric phase with parameters aR=3.208 nm, xcex1=36xc2x0, shown in alloys of composition close to Al64Cu24Fe12 in its number of atoms. This phase is a phase that approximates to the icosahedric phase. One can also mention the orthorhombic phases O2 and O3 with respective parameters a0(2)=3.83; b0(2)=0.41; c0(2)=5.26 and a0(3)=3.25; b0(3)=0.41; c0(3)=9.8 in nanometers which is formed in the alloy of composition Al63Cu8Fe12Cr12 in its number of atoms. One can further mention a phase C, of cubic structure, very often observed in coexistence with the approximating phases or true quasi-crystalline phases. This phase which is formed in certain Alxe2x80x94Cuxe2x80x94Fe and Alxe2x80x94Cuxe2x80x94Fexe2x80x94Cr alloys, consists of a superlattice, through a chemical ordering effect of the alloy elements in relation to the aluminum sites, of a phase with a CsCl structure and a lattice parameter a1=0.297 nm. One can also mention an H phase of hexagonal structure which derives directly from the C phase as the epitaxy relationships, as observed by electron microscopy demonstrate, between crystals of the C and H phases and the simple relationships which link the parameters of the crystal lattices, namely aH=32a13 (roughly 4.5%) and cH=33a1/2 (roughly 2.5%). This phase is isotypical of a hexagonal phase, designated "PHgr"AlMn, discovered in Alxe2x80x94Mn alloys containing 40% by weight of Mn. The cubic phase, its superlattices and the phases which derive from it, constitute a class of phases approximating to quasi-crystalline phases of neighboring composition. For more information about quasi-crystalline phases in the strict sense and phases approximating to them, reference can be made to EP-A-0 521 138 (J. M. Dubois, P. Cathonnet).
The quasi-crystalline alloys generally have good mechanical properties, high thermal stability and good resistance to corrosion.
The present inventors have now found that the rate of absorption of infra-red radiation of these quasi-crystalline alloys is particularly high and that they could be advantageously used in devices intended to absorb infra-red radiation.
Consequently, the objective of this invention is the use of quasi-crystalline alloys for the absorption of the infra-red radiation, and a device that absorbs the infra-red radiation, which includes an element made of a quasi-crystalline alloy.
A device according to this invention, that absorbs the infra-red radiation, is characterized in that it comprises as a coupler element for the infra-red radiation, an element made of a quasi-crystalline alloy made up of one or more quasi-crystalline phases representing at least 40% by volume of quasi-crystalline alloy, a quasi-crystalline phase being either a quasi-crystalline phase in the strict sense which has symmetries of rotation normally incompatible with the symmetry of translation, that is to say rotation axis symmetries of order 5, 8, 10 and 12, or an approximating phase or an approximating compound which is a true crystal the crystallographic structure of which remains compatible with the symmetry of translation, but which has, in the electron diffraction image, diffraction diagrams the symmetry of which is close to rotation axes 5, 8, 10 or 12.
A particularly preferred quasi-crystalline alloy is an alloy in which the quasi-crystalline phase is an icosahedric phase of point group m3 5 or a decagonal phase of the point group 10/mmm.
The quasi-crystalline alloys in which the quasi-crystalline phases represent at least 80% by volume are particularly preferred.
Among the quasi-crystalline alloys which can be used for the devices of this invention, one can mention those which show one of the following nominal compositions, which are given as an atomic percentage:
AlaCubFecXdYeIg, (I) in which X represents at least one element chosen from among B, C, P, S, Ge and Si, Y represents at least one element chosen from among V, Mo, Ti, Zr, Nb, Cr, Mn, Ru, Rh, Ni, Mg, W, Hf, Ta and the rare earths and I represents the unavoidable production impurities, 0xe2x89xa6gxe2x89xa62, 14bxe2x89xa630, 7xe2x89xa6cxe2x89xa620, 0xe2x89xa6dxe2x89xa65, 21xe2x89xa6b+c+exe2x89xa645 and a+b+c+d+e+g=100;
AlaPdbXcYdTeIg (II) in which X represents at least one metalloid chosen from among B, C, Si, Ge, P and S; Y represents at least one metal chosen from among Fe, Mn, V, Ni, Cr, Zr, Hf, Mo, W, Nb, Ti, Rh, Ru, Re; T is at least one rare earth and I represents the unavoidable production impurities; with a+b+c+d+e+f+g=100; 17xe2x89xa6bxe2x89xa630; 0xe2x89xa6cxe2x89xa68; 5xe2x89xa6dxe2x89xa615; 0xe2x89xa6exe2x89xa64; 0xe2x89xa6gxe2x89xa62;
AlaCubCOcXdYeTfIg (III) in which X represents at least one metalloid chosen from among B, C, Si, Ge, P and S; Y represents at least one metal chosen from among Fe, Mn, V, Ni, Cr, Zr, Hf, Mo, W, Nb, Ti, Rh, Ru, Re; T is at least one rare earth and I represents the unavoidable production impurities; with a+b+c+d+e+f+g=100; 14xe2x89xa6bxe2x89xa627; 8xe2x89xa6cxe2x89xa624; 28xe2x89xa6b+c+exe2x89xa645; 0xe2x89xa6fxe2x89xa64; 0xe2x89xa6dxe2x89xa6; 0xe2x89xa6gxe2x89xa62;
AlaXdYeIg, (IV) in which X represents at least one element chosen f rom among B, C, P, S, Ge, and Si, Y represents at least one element chosen from among V, Mo, Cr, Mn, Fe, Co, Ni, Ru, Rh and Pd and I represents the unavoidable production impurities; 0xe2x89xa6gxe2x89xa62, 0xe2x89xa6dxe2x89xa65, 18xe2x89xa6exe2x89xa629 and a+d+e+g=100;
AlaCubCob, (B, C)cMdNeIf (V) in which M represents at least one element chosen from among Fe, Mn, V, Ni, Cr, Ru, Os, Mo, Mg, Zn and Pd; N represents at least one element chosen from among W, Ti, Zr, Hf, Rh, Nb, Ta, Y, Si, Ge, the rare earths and I represents the unavoidable production impurities; with a+b+bxe2x80x2+c+d+e+f=100; axe2x89xa650; 0xe2x89xa6bxe2x89xa614; 0xe2x89xa6bxe2x89xa622; 0 less than b+bxe2x80x2xe2x89xa630; 0xe2x89xa6cxe2x89xa65; 8xe2x89xa6dxe2x89xa630; 0xe2x89xa6exe2x89xa64; fxe2x89xa62.
The quasi-crystalline alloys defined above are particularly suitable for the production on the one hand of coatings having a rough surface, and on the other hand coatings having high porosity, it being possible for the dimensions of the pores to be clearly greater than the wave length of the infra-red radiation. This irregularity of the surface, and especially the open pores facing the infra-red radiation constitute black bodies which increase considerably the absorption of the infra-red radiation. Taking account of the mechanical properties of these coatings, these black bodies are only sensitive to being sealed up by external agents such as dust. This disadvantage is however a minor one since the quasi-crystalline alloys form surfaces with only slight adhesive properties, which allows them to be easily cleaned. Conversely, the materials used in the devices of the prior art for absorbing infra-red radiation are very sensitive to the effects of dust which can only be removed by traditional methods of cleaning.
The quasi-crystalline alloys are therefore well suited for use as a coupler element for the infra-red radiation in the form of a layer deposited on a substrate. The layer of quasi-crystalline alloy can be made up of the quasi-crystalline alloy alone. It can also be made up of a mixture of a quasi-crystalline alloy and another material, for example, a binder.
The thickness of the layer of quasi-crystalline alloy is within a range of about ten nanometers to a few tens of micrometers, depending on the nature of the device according to the invention.
The layer of quasi-crystalline alloy can be deposited on a suitable substrate according to various methods.
A first method consists of spraying onto the substrate to be coated a quasi-crystalline alloy powder using a hot spraying device, such as a plasma torch or a blowtorch with a supersonic flame. One can also use a blowtorch with a conventional flame supplied with a mixture of oxygen and a combustible gas such as acetylene or propane, for example. When a blowtorch with a conventional flame is used, it is preferable to supply it using a flexible line which allows one, for example, to develop the quasi-crystalline structure directly in the flame, as described in EP-A-0 504 048 (J. M. Dubois, M. Ducos, R. Nury). These methods that use hot spraying allow one to obtain coatings, the thickness of which is between about 10 gm and a few hundreds of xcexcm, typically coatings whose thickness is of the order of mm.
Another technique consists of carrying out the deposition from the vapor phase. Various vapor phase deposition methods are known. By way of example, one can mention cathodic sputtering, the technique of evaporation under vacuum and laser ablation. For each of the vapor phase deposition techniques, one can use either a single source made up of a material, the composition of which will be adjusted in such a way as to obtain the desired composition on the substrate. Also several sources can be used, each corresponding to one of the elements making up the quasi-crystalline alloy. When several sources are used, either a simultaneous deposition or a sequential deposition can be made. Simultaneous deposition from several sources requires simultaneous control of several deposition flows to obtain the desired alloy composition. When successive layers are deposited from several sources, it is sometimes necessary to carry out a subsequent heat treatment in order to mix the different deposited elements and obtain the quasi-crystalline alloy. The vapor phase deposition techniques allow one to obtain layers of quasi-crystalline alloys having a very small thickness, typically less than 10 xcexcm, more particularly less than 0.3 xcexcm.
A layer of quasi-crystalline alloy can in addition be obtained by coating a substrate with a paint essentially made up of a quasi-crystalline alloy powder and an organic binder. The layers thereby obtained generally have a thickness greater than I pm, more particularly between 5 and 50 xcexcm.
The porosity and the roughness of the layers of quasi-crystalline alloy obtained depend on the method used to obtain them. The use of a plasma torch produces layers having a porosity of the order of from 5 to 10%. The layers obtained using a supersonic blowtorch are practically free of porosity. Using an oxy-gas blowtorch supplied with a powder, the particles of which have a diameter greater than 100 xcexcm, one can obtain porous layers whose mean pore diameter is between about 2 and 30 xcexcm. The layers obtained by vapor phase deposition are free of porosity. The layers obtained by application of a paint comprising a quasi-crystalline alloy powder and an organic binder, generally have a porosity of from 15 to 30%.
The coupler element for the infra-red radiation of a device according to this invention can be made up of a single grain quasi-crystal, which can be obtained for example by the growth techniques of Bridgman or Czochralsky.
A particular device according to this invention can be a bolometer, in which the quasi-crystalline alloy plays both the role of an infra-red radiation absorber and that of a resistive sensitive element. In such a device, the quasi-crystalline alloy can be in the form of a thin layer, preferably having a thickness of between 0.1 and 1 xcexcm. The quasi-crystalline alloy can also be used in the form of a single grain quasi-crystal.
Another particular device according to this invention is a temperature sensor, in which the substrate is a thermocouple, a layer of quasi-crystalline alloy enveloping the thermocouple. In such a device, the layer of quasi-crystalline alloy preferably has a thickness of between 1 and 50 xcexcm.
A device according to this invention can also be a device for photothermal conversion, such as a collector with a heat exchange fluid for solar heating (of the hot water collector type or of the air collector type), a collector for solar refrigeration or a passive collector of the Trombe wall type. In this type of device, the quasi-crystalline alloy can be deposited on substrates, the form and the nature of which vary very widely. The support for a Trombe wall is generally a concrete wall. In the collectors with a heat exchange fluid, the substrate is made up of a material that is a good conductor of heat, for example, a steel, copper or an alloy of aluminum, in the form of a plane, a profile or a groove. The layer of quasi-crystalline alloy replaces the organic paints or the deposits of finely divided metal powder used in the devices of the prior art. In the range of wavelengths of from 0.2 to 2 xcexcm, the coefficient of absorption of the infra-red radiation of a coating according to this invention is only 3% less at the most than that of a selective commercial coating such as the commercial coating MAXORB, over which nevertheless, it has all the advantages associated with a long life and good resistance to corrosion and to scratching. A coating according to the invention is as a consequence, competitive for devices for the photo-conversion of solar energy. The deposition of the quasi-crystalline alloy coating for these particular devices can be carried out by the techniques of thermal spraying, for example, using a plasma torch or a powder blowtorch. The coatings obtained in this way are intimately bonded to the substrate through an interface with excellent mechanical properties and good resistance to being torn off. This interface offers low thermal resistance to the flow of heat transmitted to the heat exchange fluid. The corrosion resistance of the coatings are particularly good as well as the mechanical strength thanks to the high hardness of the quasi-crystalline alloys and their high resistance to wear, to scratching and to abrasion. For solar energy collectors, particularly exposed collectors, these properties mean that they do not require a protective glass screen.
Another device according to this invention consists of a hot plate comprising a coating of a quasi-crystalline coating on a substrate.
A hot plate can be used in the cooking field for example in the form of a cooking surface, a grill or an oven plate. As a substrate, the bottom of a transparent cooking utensil can be used, made of Pyrex glass for example, the layer of alloy being deposited on the inside of the receptacle. For this particular use, it is desirable to use a quasi-crystalline alloy, the atomic composition of which belongs to the Group V mentioned above, in particular a composition Al≈71Cu≈9Fe≈10Cr≈10. The surface in contact with the food will be of interest for its anti-adhesive properties, the surface facing the heat source, from which it is only separated by the layer of glass which is used as a substrate, will absorb the infra-red radiation.
A hot plate can also be used for domestic heating, in the form of a heat economizer, in the form of a fire back, or in radiant heating equipment or heat accumulation apparatus.
A device according to this invention can also constitute an infra-red radiation filter, comprising a substrate transparent to the infra-red radiation, coated with a layer of quasi-crystalline alloy. The substrate can be a quartz substrate. The thickness of the quasi-crystalline alloy layer is, in this case, less than or equal to 0.3 xcexcm, and the quasi-crystalline alloy preferably comprises at least 80% by volume of a quasi-crystalline phase or a phase approximating to one.